Substituted phenoxypropionaldehyde derivates and their use as herbicidal agents

ABSTRACT

The invention relates to certain substituted phenoxypropionaldehyde derivatives, formulations of said derivatives and the use thereof for preemergence or postemergence control of noxious plants, i.e., weeds.

This is a division of application Ser. No. 797,310, filed Nov. 12, 1985,now U.S. Pat. No. 4,661,149.

FIELD OF THE INVENTION

This invention relates to certain substituted phenoxypropionaldehydederivatives, formulations of said derivatives and the use thereof forpreemergence or postemergence control of noxious plants, i.e., weeds.

DESCRIPTION OF THE INVENTION

This invention provides herbicidally active substitutedphenoxypropionaldehyde derivatives represented by the formula: ##STR1##wherein Ar is selected from: ##STR2## wherein:

W and W¹ are independently O, S or NH;

X is CY, N or N or N⊕--O⊖;

Q is N or N⊕--O⊖;

Z is CH or N;

Y is hydrogen, halogen, cyano, nitro or lower haloalkyl;

Y¹ and Y² are independently hydrogen, halogen, nitro cyano or loweralkyl, haloalkyl, alkoxy or lower alkoxy;

R is hydrogen or lower alkyl or haloakyl;

R¹ is cyano, vinyl, acetynl, dialkylphosphinyl or dialkylphosphonyl; and

R² is --OR³, --SR³ or --NR⁴ R⁵ wherein

R³ is hydrogen, C₁ to C₁₀ alkyl, cycloalkyl, haloalkyl, hydroxyalkyl,oxoalkyl, alkoxyalkyl, alkenyl, alkynyl, Ar, --COR⁶ or --CSR⁶ wherein R⁶is C₁ to C₁₀ alkyl, cycloalkyl, haloalkyl, alkenyl, alkynyl, amino, Ar,--COOR⁷ or --COSR⁷ wherein R⁷ is hydrogen, alkali metal,

C₁ to C₁₀ alkyl, cycloalkyl, haloakyl, alkenyl, alkynyl or Ar; and

R⁴ and R⁵ are independently hydrogen or lower alkyl.

Preferred compounds of the invention are those wherein R is lower alkyl,R¹ is cyano and R² is --OR³.

The compounds of the invention may be prepared using techniques andstarting materials known and available to those skilled in the art, andpreparation of certain of the invention compounds are illustrated by thefollowing Examples, wherein invention compounds of the following formulaare prepared: ##STR3##

    ______________________________________                                        Ex-                                                                           am-                                                                           ple  X      Y.sup.1                                                                              R.sup.1     R.sup.2                                        ______________________________________                                        I    CH     --Cl   --CN        --O--COO--C.sub.2 H.sub.5                      II   CH     --Cl   --CN        --O--COCH.sub.2 Cl                             III  N      --H    --CN        --O--COO--C.sub.2 H.sub.5                      IV   CH     --Cl   --CN        O--CO--CH.sub.3                                V    CH     --Cl   --CN        --O--CO--COO--C.sub.2 H.sub.5                  VI   CH     --Cl   --CN        --O--COS--C.sub.2 H.sub.5                      VII  CH     --Cl   --CN        --OCH.sub.3                                    VIII CH     --Cl   --P═O--(OCH.sub.3).sub.2                                                              --OH                                           ______________________________________                                    

EXAMPLE I

Preparation of:2-ethoxycarbonyloxy-3-[4-(2-chloro-4-trifluoromethylphenoxy)phenoxy]butyronitrile.

To a 100 milliliter flask provided with magnetic stirring bar and adrying tube were charged 0.5 gram of2-[4-(2-chloro-4-trifluoromethylphenoxy) phenoxy]propionaldehyde, 0.5gram of sodium cyanide, 0.12 gram of tetrabutyl ammonium hydrogensulfate, 30 milliliters of methylene chloride and 0.2 milliliter ofethyl chlorocarbonate. After stirring overnight at room temperature, TLCanalysis indicated the presence of a considerable amount of unreactedstarting material so an additional 0.5 gram of sodium cyanide and 0.2milliliter of ethyl chlorocarbonate were added and stirring wascontinued for 2.5 hours after which time an additional 0.2 milliliter ofethyl chlorocarbonate was added. After stirring an additional hour TLCindicated presence of some starting material so 1.0 gram of potassiumcyanide and 0.1 gram of 18-crown-6 were added. After stirring at roomtemperature, an additional 1.5 hours, the reaction mixture wastransferred to a separatory funnel, diluted with 150 milliliters ofdiethyl ether and washed with 4×50 milliliter portions of water. Theorganic layer was dried and evaporated affording about 1.0 gram of abrown, viscous residue. The residue was dissolved in methylene chlorideand eluted over silica gel using methylene chloride as the eluent. Thefirst four 50 milliliter fractions were combined and evaporatedaffording about 0.6 gram of colorless, gummy material confirmed by PMRanalysis as the desired product.

EXAMPLE II

Preparation of:2-chloroacetateoxy-3-[4-(2-chloro-4-trifluoromethylphenoxy)phenoxy]butylronitrile.

A mixture of 0.3 gram of2-[4-(2-chloro-4-trifluoromethylphenoxy)phenoxy]propionaldehyde, 0.6grams of sodium cyanide, 0.06 grams of tetrabutyl ammonium hydrogensulfate, 0.1 grams of chloroacetyl chloride and 30 milliliters ofmethylene chloride was stirred at room temperature and under a nitrogenblanket for about 17 hours. Since TLC analysis indicated the presence ofsubstantial unreacted starting material, 1.0 gram of powdered sodiumcyanide and 0.1 gram of chloroacetyl chloride were added and stirringcontinued for 1.5 hours. Since TLC analysis still indicated someunreacted starting material and additional 0.1 gram of chloroacetylchloride was added and stirring continued for 2 hours at roomtemperature. The reaction mixture was then diluted with 100 millilitersof diethyl ether and washed consecutively with 2×40 milliliter portionsof water, 2×40 milliliter portions of dilute aqueous sodium carbonateand 2×40 milliliter portions of water. The organic phase was dried andevaporated affording about 0.4 gram of colorless, viscous materialconfirmed by PMR and MS analyses as the desired product.

EXAMPLE III

Preparation of:2-ethoxycarbonyloxy-3-[4-(5-trifluoromethyl-2-pyridyloxy)phenoxy]butyronitrile.

A mixture of 0.28 grams of 3-[4-(5-trifluromethyl-2-pyridyloxy)phenoxy]propionaldehye, 1.0 gram of powdered sodium cyanide, 0.1 gram oftetrabetyl ammonium hydrogen sulfate, 0.2 milliliter of ethylchlorocarbonate and 40 milliliters of methylene chloride was stirredovernight at room temperature under a nitrogen blanket. The reactionmixture was then diluted with 50 milliliters of methylene chloride andwashed consecutively with 2×40 milliliter portions of water, 2×40milliliter portions of saturated aqueous sodium bicarbonate and 2×40milliliter portions of water. The organic phase was dried over anhydroussodium sulfate and evaporated affording about 0.42 gram of viscous,gummy residue. The residue was eluted over silica gel using methylenechloride as the eluent, 50 milliliter fractions being collected andanalyzed by TLC. Fractions 5 through 11 were combined and evaporatedaffording about 0.3 gram of colorless viscous material confirmed by NMRand MS analyses as the desired product.

EXAMPLE IV

Preparation of:2-acetyloxy-3-[4-(2-chloro-4-trifluoromethylphenoxy)phenoxy]butyronitrile.

A mixture of 0.5 gram of2-[4-(2-chloro-4-trifluoromethylphenoxy)phenoxy]propionaldehyde, 1.0gram of potassium cyanide, 0.2 gram of 18-crown-6 and 40 milliliters ofmethylene chloride was stirred for one hour at room temperature at whichtime 0.1 milliliter of acetyl chloride was added, followed by anadditional 0.1 milliliter of acetyl chloride about 40 minutes later.After stirring overnight, TLC analysis indicated the presence of traceamounts of unreacted starting material, so two additional 0.1 milliliterportions of acetyl chloride were added and stirring continued, at roomtemperature, for about a total of 22 hours. The reaction mixture wasthen evaporated, the residue was taken up in 150 milliliters of diethylether and washed with 4×40 milliliter portions of water. The organicphase was dried and evaporated and the resulting viscous residue waseluted over silica gel using a 1:2 V/V mixture of hexane:methylenechloride as the eluent. 50 milliliter fractions of eluent were collectedand analyzed by TLC analysis. The fractions containing the desiredproduct were combined and evaporated affording about 0.45 gram ofcolorless viscous liquid confirmed by spectral analysis as the desiredproduct.

EXAMPLE V

Preparation of:2-ethyloxalateoxy-3-[4-(2-chloro-4-trifluoromethylphenoxy)phenoxy]butyronitrile.

A mixture of 0.6 gram of3-[4-(2-chloro-4-trifluoromethylphenoxy)phenoxy]propionaldehyde, 1.2gram of potassium cyanide, 0.2 gram of 18-crown-6 and 40 milliliters ofmethylene chloride were stirred at room temperature for one hour atwhich time 0.3 milliliter of ethyl oxalylchloride was added and stirringwas continued overnight. An additional 0.3 milliliter of ethyloxalylchloride was added and stirring was continued another 4 hours. Thereaction mixture was then evaporated, taken up in 150 milliliters ofdiethyl ether and washed with 4×50 milliliter portions of water. Dryingand evaporation afforded about 0.8 gram of viscous liquid residue. Theresidue was purified over silica gel using methylene chloride as theeluent, 50 milliliter fractions being collected and analyzed by TLC. Thefractions containing the desired product were combined and evaporatedaffording about 0.3 gram of material, confirmed by spectral analysis asthe desired product.

EXAMPLE VI

Preparation of:2-thioethylcarbonyloxy-3-[4-(2-chloro-4-trifluoromethylphenoxy)phenoxy]butyronitrile.

A mixture of 0.6 gram of2-[4-(2-chloro-4-trifluoromethylphenoxy)phenoxy]propionaldehyde, 0.35gram of potassium cyanide, 0.2 gram of 18-crown-6 and 30 milliliters ofmethylene chloride were stirred at room temperature overnight afterwhich time 0.3 milliliter of thioethyl carbonyl chloride was added andstirring was contained another 4 hours. The reaction mixture was thenevaporated, the residue was taken up in 20 milliliters of methylenechloride and filtered through silica gel. The filtrate was evaporatedaffording about 0.6 gram of gummy colorless material shown, by TLC andPMR analyses, to be a mixture containing the desired product. Subsequentpurification by adsorption on silica gel, using a 1:1 V/V mixture ofhexane:methylene chloride as the eluent, afforded about 0.3 gram ofmaterial identified by spectral analysis as the desired product.

EXAMPLE VII

Preparation of:2-methoxy-3-[4-(2-chloro-4-trifluoromethylPhenoxy)phenoxy]butyronitrile.

A mixture of 0.6 gram of2-[4-(2-chloro-4-(2-chloro-4-trifluoromethylphenoxy)phenoxy]propionaldehyde,0.35 gram of potassium cyanide 0.2 gram of 18-crown-6 and 30 millilitersof methylene chloride was stirred at room temperature under a nitrogenblanket for about 5 hours, at which time TLC analysis indicated completeconsumption of starting material. One milliliter of methyl iodide and0.5 gram of potassium carbonate were then added and stirring at roomtemperature was continued for about 65 hours. TLC analysis indicated thepresence of some starting material so an additional 1.0 milliliter ofmethyl iodide was added and stirring was continued another 24 hours. Thereaction mixture was then evaporated, the residue was taken up in 150milliliters of diethyl ether and washed with 3×30 milliliter portions ofwater. Solvent was evaporated and the residue was purified by adsorptionon silica gel and eluted with 1:1 V/V mixture of hexane:methylenechloride. 50 milliliter fractions being collected and analyzed by TLC.Subsequent combination and evaporation of the appropriate fractionsafforded 0.25 gram of material. Since spectral analysis of this materialindicated it to be a mixture of compounds, the same was subjected topreparative TLC purification to isolate the desired product.

EXAMPLE VIII

Preparation of:dimethyl-2-hydroxy-3-[4-(2-chloro-4-trifluoromethylphenoxy)phenoxy]propylphosphonate.

To a stirred mixture of 2.6 grams of3-[4-(2-chloro-4trifluoromethylphenoxy)phenoxy]propionaldehyde and 0.88grams of dimethyl phosphite was added 2.9 grams of potassium fluoride.Stirring was stopped and the mixture solidified in about 10 minutes.After standing for about 2 hours, the solidified reaction mixture wastaken up in 50 milliliters of methylene chloride and filtered. Thefiltrate was evaporated affording a viscous, colorless residue. Theresidue was adsorbed on silica gel and eluted with methylene chlorideand ethyl acetate. Evaporation of the ethyl acetate fractions affordedabout 3.0 grams of material identified by spectral analysis as thedesired product.

EXAMPLES IX to XII

Following the procedures described in the foregoing Examples but using3-[4-(5-trifluoromethyl-2-pyridyloxy)phenoxy]-2-hydroxy butyronitrile(prepared in situ in Example III) as a starting material, the followingcompounds were also prepared:

IX. The compound,2-phenoxycarbonyl-3-[4-(5-trifluoromethyl-2-pyridyloxy)phenoxy]butyronitrile,by reaction of said starting material with phenyl chloroformate.

X. The compound,2-acetyloxy-3-[4-(5-trifluoromethyl-2pyridyloxy)phenoxy]butyronitrile,by reaction of said starting material with acetylchloride.

XI. The compound,2-methyloxycarbonyloxy-3-[4-(5-trifluoromethyl-2-pyridyloxy)phenoxy]butyronitrile,by reaction of said starting material with methylchloroformate.

XII. The compound,2-allyloxycarbonyloxy-3-[4-(5-trifluormethyl-2-pyridyloxy)phenoxy]butyronitrile,by reaction of said starting material with allyl chloroformate.

Although the invention has been illustrated by the foregoing Exampleswith regard to the preparation of certain compounds within the scope ofthe invention, it is to be understood that other compounds within thescope of the invention may readily be prepared by those skilled in theart simply by varying the choice of starting materials and using thesame or similar techniques.

Weed control in accordance with this invention is effected by applyingto the soil prior to emergence of weeds therefrom or to the plantsurfaces subsequent to emergence from the soil, a herbicidally effectiveamount of a compound of this invention. It is, of course, to beunderstood that the term "a compound of this invention" also includesmixtures of such compounds or a formulation containing a compound ormixture of compounds of this invention.

The term "herbicidally effective amount" is that amount of a compound ofthis invention required to so injure or damage weeds such that the weedsare incapable of recovering following application while not causingsubstantial injury to any valuable crop amongst which the weeds might begrowing. The quantity of a compound of this invention applied in orderto exhibit a satisfactory herbicidal effect may vary over a wide rangeand depends on a variety of factors, such as, for example, hardiness ofa particular weed species, extent of weed infestation, climaticconditions, soil conditions, method of application, and the like.Typically, one or less pound per acre of a compound of this inventionwould be expected to provide satisfactory weed control, although in someinstances application rates in excess of one pound per acre, e.g., up to2 or more pounds per acre might be required. Of course, the efficacy ofa particular compound against a particular weed species may readily bedetermined by routine laboratory or field testing in a manner well knownto the art. It is expected that satisfactory weed control can be had ata rate of application in the range of 0.1 to 1.0 pound per acre.

Of course, a compound of this invention can be formulated according toroutine methods with any of several known and commonly used herbicidaldiluents, adjuvants and carriers. The formulations can contain liquidcarriers and adjuvants such as organic solvents, as well as emulsifiers,stabilizers, dispersants, suspending agents, spreaders, penetrants,wetting agents and the like. Typical carriers utilized in dryformulations include clay, talc, diatomaceous earth, silica and thelike. Preferred formulations are those in the form of wettable powders,flowables, dispersible granulates or aqueous emulsifiable concentrateswhich can be diluted with water at the site of application. Also, dryformulations such as granules, dusts, and the like, may be used.

When desired, a compound of this invention can be applied in combinationwith other herbicidal agents in an effort to achieve even broadervegetative control. Typical herbicides which can be convenientlycombined with Formula I compound include atrazine, hexazinone,metribuzin, ametryn, cyanazine, cyprazine, prometon, prometryn,propazine, simazine, terbutryn, propham, alachlor, acifluorfen,bentazon, metolachlor and N,N-dialkyl thiocarbamates such as EPTC,butylate or vernolate. These, as well as other herbicides described, forexample, in the Herbicide Handbook of the Weed Science Society ofAmerica, may be used in combination with a compound or compounds of theinvention. Typically such formulations will contain from about 5 toabout 95 percent by weight of a compound of this invention.

The herbicidal formulations contemplated herein can be applied by any ofseveral methods known to the art. Generally, the formulation will beapplied as an aqueous spray. Such application can be carried out byconventional ground equipment, or if desired, the sprays can be aeriallyapplied. Soil incorporation of such surface applied herbicides isaccomplished by natural leaching, and is of course facilitated bynatural rainfall and melting snow. If desired, however, the herbicidescan be incorporated into the soil by conventional tillage means.

Compounds of this invention have been found especially useful forcontrolling grassy weeds but could be used for preemergence andpostemergence control of a wide variety of grassy weeds. Typical of thevarious species of vegetative growth that may be controlled, combated,or eliminated are, for example, annuals such as foxtail, crabgrass,field pennycress, ryegrass, goose grass, wild oats, barnyardgrass, hempnettle, spurge, pondweed, cheatgrass, fall panicum, witchgrass,watergrass, and similar annual grasses and weeds. Biennials that may becontrolled include wild barley, campion, and the like. Also controlledby the compounds of this invention may be perennials such as quackgrass,Johnsongrass, horsetail, cattail, and the like.

The compounds prepared as described in the Examples were individuallytested for herbicidal efficacy, against a variety of grassy weedspecies, under controlled laboratory conditions of light, humidity andtemperature. A solvent solution of each compound was applied, bothpreemergence and postemergence, to test flats containing the variousweed species, and herbicidal efficacy was determined by periodic visualinspection, after application of the compounds vis a vis an untreatedcontrol. Herbicidal efficacy was determined on a Numerical Injury Rating(NIR) scale of from 0 (no injury) to 10 (all plants dead). A NIR ratingof 7-9 indicates severe injury; a NIR rating of 4-6 indicates moderateinjury, i.e., plant growth is reduced to the extent that normal growthcould be expected, but only under ideal conditions; and a NIR rating of1-3 indicates slight injury.

The following tables gives the individual and average preemergence(Table I) and postemergence (Table II) NIR determined for the compoundsprepared as described in Examples I to VIII on the grassy (GR) weedspecies to which the compounds were applied, at the indicated rate ofapplication in pounds per acre. The NIR was determined three weekssubsequent to application.

                  TABLE I                                                         ______________________________________                                        Compd:  I      II    III   IV   V     VI  VII  VIII                           ______________________________________                                        YLFX    10     7     10    10   9     9   9    9                              CBGS    10     7     10    10   10    9   9    10                             JNGS    10     7     10    10   9     9   4    8                              WOAT    8      5     3     7    7     8   4    5                              BNGS    --     8     10    8    10    8   3    8                              Rate    1.0    1.0   0.5   0.9  1.0   1.0 0.64 2.0                            Average 9.5    6.8   8.6   9.0  9.0   8.6 5.8  8.0                            ______________________________________                                    

                  TABLE II                                                        ______________________________________                                        Compd:    I      II       III IV    V    VII                                  ______________________________________                                        YLFX      10     7        8   7     4    10                                   JNGS      8      7        7   7     6    10                                   WOAT      7      7        1   6     1    6                                    BNGS      10     --       9   --    10   10                                   Rate      5.0    1.0      1.1 5.0   1.0  0.64                                 Average   8.8    7.0      6.3 6.7   5.3  9.0                                  ______________________________________                                    

The grassy weeds used in the screening test were barnyardgrass (BNGS),large crabgrass (CBGS), Johnsongrass (JNGS), wild oats (WOAT) and yellowfoxtail (YLFX).

Although the invention has been described in considerable detail by theforegoing, it is to be understood that many variations may be madetherein by those skilled in the art without departing from the spiritand scope thereof as defined by the appended claims.

I claim:
 1. A compound of the Formula: ##STR4## wherein y¹ and Y² areindependently hydrogen, halogen, nitro, cyano, or lower alkyl, haloalkylor alkoxy;W is oxygen or sulfur; R is hydrogen or lower alkyl or alkoxy;R¹ is cyano, vinyl, acetynyl, lower dialkylphosphinyl ordialkylphosphonyl; R³ is hydrogen, or up to C₁₀ alkyl, cycloalkyl,haloalkyl, hydroxyalkyl, oxoalkyl, alkoxyalkyl, alkenyl, alkynyl or--COR⁶ or --CSR⁶ wherein R⁶ is up to C₁₀ alkyl, cycloalkyl, haloalkyl,alkoxy, alkenyl, alkynyl, amino, --COOR⁷ or --COSR⁷ wherein R⁷ ishydrogen, alkali metal, up to C₁₀ alkyl, cycloalkyl, haloalkyl, alkenylor alkynyl.
 2. A compound of claim 1 of the Formula ##STR5## wherein Y¹is hydrogen or halogen;R is lower alkyl; and R³ is hydrogen, up to C₁₀alkyl or haloalkyl or --COR⁶ or --CSR⁶ wherein R⁶ is up to C₁₀ alkyl oralkoxy or --COOR⁷ or --COSR⁷ wherein R⁷ is hydrogen alkali metal or upto C₁₀ alkyl.
 3. A herbicidal composition containing an agronomicallyacceptable carrier and a herbicidally effective amount of a compound ormixture of compounds defined in claim
 1. 4. In a method of controllingweeds wherein a herbically effective amount of herbicide is applied to agrowth medium prior to emergence of weeds therefrom or to the weedssubsequent to emergence from the growth medium, the improvment residingin using as the herbicide a compound or mixture of compounds as definedin claim 1.